Liquid-Vapor Equilibria at 250.

00K for Systems Containing Methane,

Ethane, and Carbon Dioxide
Juan Davalos,' Wayne R. Anderson,2 Robert E. Phelps, and Arthur J. Kidnay3
Department of Chemical and Petroleum-Refining Engineering, Colorado School of Mines, Golden, Colo. 8040 1

Liquid-vapor equilibria for the binary systems methaneethane, methane-carbon dioxide, and ethane-carbon
dioxide and for the ternary system of methane-ethanecarbon dioxide were measured at 250.00K and at pressures
of 13-80 atm. Additional liquid-vapor measurements are
reported for methane-carbon dioxide at 230.00 and
270.00K.

The increased emphasis of recent years in the low-temper-,

ature processing of natural gas has resulted in the need for
the phase equilibrium properties of light hydrocarbon-carbon
dioxide systems. Some experimental data are available for
the binary systems composed of methane, ethane, and carbon dioxide, but no measurements have been made on the
ternary system. Thus, the work reported here will be of considerable value to both the thermodynamicist and the process
design engineer.
Previous Experimental Work
Experimental phase equilibrium measurements for the binary systems methane-ethane, methane-carbon dioxide, and
ethane-carbon dioxide prior to 1973 have been listed in a recent review paper (9).
Table I summarizes all the recent work
not reported in ref. 9. There are no experimental data available for the ternary system.
Experimental Equipment and Procedure
The basic equipment and procedures have been discussed
in some detail previously (2); thus, only a brief description of
two recent modifications will be presented here. The first
modification was the conversion of the single-pass equilibrium
system into a closed-loop, vapor-recirculation system by the
addition of a diaphragm metering pump and a gas sample
loop. This change was made to allow a more rapid attainment
of equilibrium. The second modification was the replacement
of the copper cell and its equilibrium trays with an empty
stainless-steel cell of approximately the same volume. The
modified system was very similar in principle to that used by
Miller et al. ( 11).
The system pressures were measured with two Heise
Bourdon-tube gauges having ranges of 0-34 and 0-100 atm.
The 0-100 atm gauge had been calibrated earlier with a
dead-weight gauge. The temperature was measured on IPTS68 with a calibrated platinum resistance thermometer. The
liquid and vapor samples were analyzed on a gas chromatograph equipped with a thermal conductivity detector.
Vapor-pressure measurements were made on the ethane
and the carbon dioxide used in the program, and the values
obtained are compared with the best available literature
values in Table II.
The values of Meyers and Van Dusen ( IO) were adjusted
to IPTS-68; no adjustments were necessary for the ethane
values from Goodwin (5). The discrepancy observed at

270.00K is believed due to some slight impurity present during

that particular measurement or to operator reading error,
since all other values are in excellent agreement. The data of
Table II verify the accuracy of the temperature and pressure
measurements and the purity of the ethane and carbon dioxide. The methane was Matheson ultrahigh purity grade with a
maximum impurity of 0.03% .
Based on observations and calibrations, it is believed that
the temperature measurements are accurate to fO.OlK,the
pressure measurements accurate to f0.03 atm (34 atm or
less) and f0.05atm (34-100atm), and the compositions accurate to f1.5% of the reported values.
Results
The results of the experimental program are presented in
Table Ill and IV and in Figures 1-6.
The binary data were tested for consistency in two ways.
First, three graphical methods were employed to evaluate the
reliability of the low-pressure results for both the liquid and
vapor phases, and second, the numerical method of orthogonal collocation was used for the high-pressure data.
The graphical methods were: a plot of the enhancement
factor (defined as y1P/pl0)vs. P; a plot of KIP vs. P; and a
graph of x2 against (P p l 0 ) .The enhancement factor provides an excellent check on the reliability of the low-pressure
vapor-phase measurements, since the data must be on a
smooth curve extrapolating to a value of one at the ordinate.
The plot of K I P against P provides a check of both the liquid
and vapor-phase measurements at low pressures, since the
data must be on a smooth curve extrapolating to a value of
p l 0 . Finally, the reliability of the liquid-phase measurements
may be judged by plotting liquid composition vs. pressure dif-

Table I . Summary of Recent Phase Equilibrium Measurements for

Binary Systems

System
CH,-C, H,
CH,-CO,
C0,-C, H,

130
253, 273, 288
223-293
242-283
222-289
283-293
253
289

Press
range, atm

Lit

1-3
26-84
5-56
10-49
7-56
30-62
14-23
35-56

Table I I. Comparison of Vapor-Pressure Measurements on Ethane

and Carbon Dioxide with Literature Values

Vapor press, atm

Component
CO,

'Present address, ENKADOR, Quito, Ecuador.

*Present address, TOSCO. Golden, Colo.
3To whom correspondence should be addressed

Temp range, K

C,H,

Temp, K

This
investigation

230.00
250.00
270.00
250.00

8.80
17.62
31.53
12.85

Meyers
and Van Goodwin
Dusen ( 1 0 )
(5)
8.818
17.620
31.611

...

...
...

...
12.85

Journal of Chemical and Engineering Data, Vol. 2 1, No. 1, 1976

81

Table I l l . Vapor-Liquid Equilibria for Binary Systems

System
press,
atm YCH,
12.85
15.10
22.00
22.50
32.50
34.00
45.00
55.20
65.70
67.50

XCH,

Yc,H,

XC,H,

C H,-C, H 6 , 25 O.OOK
0.00
0.00
1.00
1.00
0.134 0.024 0.866 0.976
0.365 0.089 0.635 0.911
0.383 0.097 0.617 0.903
0.540 0.196 0.460 0.804
...
0.554
0.446
0.643 0:320 0.357 0.680
0.673 0.426 0.327 0.574
0.673 0.546 0.327 0.454
Single-phase region

System
press,
atm Y C H ,

X ~ H ,

ycO,

xco,

KCH, Kc,H,

5.702
4.101
3.948
2.755

1.00
0.887
0.697
0.683
0.572

2:009
1.580
1.233

0.525
0.570
0.720

KCH,

...

Kco,

17.62
20.00
23.32
24.68
30.00
40.00
50.00

230.00K
0.00
0.00
1.00
1.00
...
0.399 0.027 0.601 0.973 14.67
0.525 0.050 0.475 0.950 10.50
0.683 0.115 0.317 0.885
5.94
0.728 0.170 0.277 0.830
4.28
0.751 0.235 0.249 0.765
3.20
2.43
0.764 0.318 0.236 0.686
0.752 0.397 0.248 0.603
1.a9
0.762 0.394 0.238 0.606
1.93
0.757 0.472 0.243 0.528
1.60
0.751 0.534 0.249 0.466
1.41
0.732 0.526 0.268 0.474
1.39
0.730 0.543 0.270 0.457
1.34
0.725 0.561 0.275 0.439
1.29
0.716 0.584 0.284 0.416
1.23
Single-phase region
CH,-CO,, 250.00K
0.00
0.00
1.00
1.00
...
0.104 0.010 0.896 0.990 10.40
9.70
0.223 0.023 0.777 0.977
. ..
0.254
0.746
...
0.361 0:053 0.639 0.947
6.81
0.491 0.105 0.509 0.895
4.68
3.46
0.575 0.166 0.425 0.834

1.00
0.6 18
0.500
0.398
0.328
0.325
0.344
0.4 11
0.393
0.461
0.534
0.565
0.591
0.626
0.683
1.oo
0.905
0.795

*..

0.6 75
0.569
0.510

Table I V . Vapor-Liquid Equilibria for Ternary System CH,-C,H,-CO,

System
press,
atm
2 1.oo

25.00

30.00

82

YCH,

0.0265
0.1728
0.1602
0.2500
0.0288
0.0374
0.0400
0.0235
0.3521
0.3264
0.1901
0.1323
0.1387
0.1701
0.2464
0.4021
0.2605
0.2580
0.3025
0.2630
0.3448

YC2H6

0.4432
0.5700
0.5615
0.6200
0.2007
0.1700
0.1600
0.2154
0.5377
0.5264
0.4148
0.2937
0.2601
0.1623
0.4730
0.4531
0.2845
0.2420
0.0935
0.2270
0.4182

XCH,

YCH,

y ~ O ,

CH,-CO,,

.. .

CH,-CO,,

8.80
15.00
20.00
32.00
40.00
48.00
55.00
61.10
62.00
65.00
68.00
68.44
69.08
69.81
70.47
70.81

System
press,
atm

YCO,

XCH,

0.5303
0.2572
0.2783
0.1300
0.7715
0.7926
0.8000
0.761 1
0.1 102
0.1472
0.3951
0.5740
0.6012
0.6676
0.2806
0.1448
0.4550
0.5000
0.6040
0.5100
0.2370

0.0033

...
...

0.605 0.237 0.395

0.615 0.326 0.385
0.605 0.400 0.395
0.564 0.405 0.436
0.558 0.446 0.442
Single-phase region

31.53
35.09
36.53
39.75
41.59
49.97
57.81
69.29
79.58
84.08
84.81

0.00
0.00
1.00
0.083 0.014 0.917
0.108 0.018 0.892
0.162 0.032 0.838
0,190 0.040 0.810
0.282 0.077 0.718
0.353 0.113 0.647
0.405 0.166 0.595
0.411 0.260 0.589
0.375 0.319 0.625
Single-phase region

CH,-CO,,

270.00K
1.00
0.986
0.982
0.968
0.960
0.923
0.887
0.834
0.740
0.681

yC02

XC,Hb

~~~

XCO,

KCO,

2.55
1.a9
1.51
1.39
1.25

0.518
0.571
0.658
0.733
0.798

...

1.oo
0.930
0.908
0.866
0.844
0.778
0.730
0.714
0.795
0.919

6.09
5.95
5.09
4.78
3.68
3.13
2.43
1.58
1.17

KC,Hb

KC02

C,H6-CO,,
12.85
14.23
15.68
16.93
18.04
19.23
20.03
20.56
20.99
21.07
20.80
19.99
19.40
18.51
17.62

1.00
0.8885
0.7774
0.6991
0.6303
0.5526
0.4964
0.4478
0.3735
0.3198
0.2533
0.1783
0.1304
0.0622
0.00

1.00
0.9556
0.8965
0.8320
0.7755
0.6917
0.6020
0.5308
0.4010
0.3100
0.2092
0.1171
0.0740
0.0299
0.00

250.00K
0.00
0.00
0.1115 0.0444
0.2226 0.1035
0.3009 0.1680
0.3697 0.2245
0.4447 0.3083
0.5056 0.3980
0.5522 0.4692
0.6265 0.5990
0.6802 0.6900
0.7467 0.7908
0.8217 0.8829
0.8696 0.9260
0.9378 0.9701
1.00
1.00

1.00
0.9298
0.8672
0.8403
0.8128
0.7989
0.8213
0.8436
0.9314
1.032
1.211
1.523
1.762
2.080

...

...
2.511
2.151
1.791
1.647
1.451
1.270
1.177
1.046
0.9858
0.9442
0.9307
0.9391
0.9667
1.000

at 250.00K

XC2H6

0.4512

xco,
0.5455

...

...

0.0352

0.i898

01
: 5
i 0

0.0020
0.0022

0.1'198
0.0986

0.8782
0.8992

0.0999
0.0950
0.0508
0.0298
0.0282
0.0247

0.8'18 9
0.8097
0.5792
0.3157
0.2662
0.1392

0.0812
0.0953
0.3700
0.6545
0.7056
0.8361

...

0.'1351
0.0705
0.0685

0.7350
0.3741
0.3250

0.0520
0.1203

0.2495
0.6652

Journal of Chemical and Engineering Data, Vol. 21, No. 1, 1976

250.00K
0.763
0.674
0.600
0.595
0.554

60.00
70.00
77.00
78.50
79.88
80.70

System
press,
atm YC,H6

KCH,

XCO,

KCH,

8.030

...
...
7.102
...

KC2H6

0.9823

...
...

KCO,

0.9721

...

0.7850

o.ib29

1.419
1.623

0.902 5
0.8897

3.525
3.436
3.742
4.439
4.918
6.887

1.357
1.545
1.068
0.8770
0.8520
0.7985

...

...

0.6566
0.650 1
0.7162
0.9303
0.9771
1.1660

0.1300
0.5554
0.6064

2.976
3.695
3.766

0.6'165
0.7605
0.7446

1.1138
0.8192
0.8245

0.7085
0.2 14 5

5.058
2.966

0.9098
0.6287

0.7198
1.1050

...

...

18.70
18.18

...

...

...

...

...

...

...
...

ference and determining if the data lie on a smooth curve (or

a straight line at very low concentrations) through the origin.
The results of these graphical tests applied to the data of
Table 111 confirm the internal and thermodynamic consistency
of the low-pressure measurements.
A good indication of the reliability of the high-pressure data
may be obtained by application of the numerical method of
orthogonal collocation, as suggested by Christiansen and Fredenslund (3).This method tests the reliability of high-pressure
vapor-liquid data by using the measured values of T, P, and x
to calculate y, and then comparing the calculated and experimental y values. The application of their method to the CHIC2He and the C2Hs-CO2 data of Table 111 results in average
differences between the calculated and experimental y
values for the two systems of 0.85and 0.37%, respectively,
again confirming the consistency of the data.
The isotherms of methane-ethane and methane-carbon
dioxide are typical for systems having one component above
its critical point. The estimated critical pressures for these
isotherms are: methane-ethane, 67.4 atm at 250.00K; methane-carbon dioxide, 70.7,80.6, and 84.7 atm at 230.00,
250.00, and 270.00K, respectively. These values are in good
agreement with critical locus values reported by previous investigators (9).
The ethane-carbon dioxide system exhibits atypical behav-

2SK

0.

0.2

0.4

0.6

0.8

1.0

MOLE FRACTION METHANE

Figure 1. Liquid-vapor equilibria in methane-ethane system

22
24[

/-\

MOLE FRACTON CARBON DIOXIDE

Figure 3. Liquid-vapor equilibria in carbon dioxide-ethane system at

250.00K

01

0.2
0.4
0.6
Q8
MOLE FRACTION METHANE

1.0

Flgure 2. Liquid-vapor equilibria in methane-carbon dioxide system

Flgure 4. Ternary system at 21.O atm and 250.00K

Journal of Chemical and Engineering Data, Vol. 21, No. 1, 1976

83

METHANE

METHAN

Flgure 5. Ternary system at 25.0 atm and 250.00K

Flgure 6. Ternary system at 30.0 atm and 250.00K

ior in the form of an azeotrope at 21.0 atm and a carbon

dioxide mole fraction of 0.67, values that are in excellent
agreement with Fredenslund and Mollerup (4).
An interesting feature of the ternary system is the behavior
of the minimum in the vapor curve of Figures 4-6. A graph of
pressure vs. percent ethane at the minimum in the vapor
curve is a straight line beginning at the C2He-CO2 azeotrope
at 2 1.OO atm.

Acknowledgment
The authors are grateful to W. R. Parrish of the National
Bureau of Standards for assistance in applying the numerical
orthogonal collocation method to the data.

Nomenclature
K = y/x
P = total system pressure
po = vapor pressure
T = temperature
x = liquid-phase mole fraction
y = vapor-phase mole fraction

84

Journalof Chemicaland Engineering Data, Vol. 21, No. 1, 1976

Literature Cited
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(2) Baughman. G. L., Westhoff, S. P., Dincer, S..Duston. D. D., Kidnay. A.
J.,J. Chem. Thermodyn., 6, 1121 (1974).
(3) Christiansen, L. J., Fredenslund, A,, AlChEJ., 21, 49(1975).
(4) Fredenslund. A., Mollerup, J.. J. Chem. Soc., Faraday Trans. I, 70, 1653
(1974).
(5) Goodwin, R. D., Provisional Values for the Thermodynamic Functions of
Ethane, NBSlR 74-398. National Bureau of Standards, 1974.
(6) Gugnoni, R. J., Eldridge, J. W., Okay, V. C.. Lee, T. J., AlChEJ.. 20, 357
(1974).
(7) Hamam, S.E.M., Lu, B.C.-Y., Can. J. Chem. Eng.. 52, 283 (1974).
(8) Khazanova. N. E., Lesnevskaya, L. S., Zhakarova, A. V., Khim. Prom.
USSR, 5,44 (1966).
(9) Kidnay, A. J., Hiza, M. J., Miller, R. C., Cryogenics, 13, 575 (1973).
(10) Meyers. C. H., Van Dusen, M. S., J. Res. Nat. Bur. Stand., 10, 381
(1933).
(11) Miller, R. C., Kidnay, A. J., Hiza, M. J., J. Chem. Thermodyn..4, 807
(1972).
(12) Nagahama, K., Konishi. H., Hoshino, D., Hirata. M.,J. Chem. Eng. Jpn..
7, 323 (1974).
(13) Robinson, D. B., Kaka, H., paper presented at the Gas Processors Association Convention, Denver, Colo., August 1974.
(14) Yu, P., Lu. 6.C.-Y., "Advances in Cryogenic Engineering." Vol 20, K. D.
Timmerhaus, Ed., Plenum Press, New York, N.Y.. in press.
Received for review April 7, 1975. Accepted July 16, 1975. Financial support
by the National Science Foundation under Grant GK-24745.